CN107240695B - Preparation method of edge-rich graphene-metal composite electrode material and composite electrode material - Google Patents
Preparation method of edge-rich graphene-metal composite electrode material and composite electrode material Download PDFInfo
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- CN107240695B CN107240695B CN201710562059.3A CN201710562059A CN107240695B CN 107240695 B CN107240695 B CN 107240695B CN 201710562059 A CN201710562059 A CN 201710562059A CN 107240695 B CN107240695 B CN 107240695B
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Abstract
The invention discloses a preparation method of an edge-rich graphene-metal composite electrode material and the composite electrode material, wherein the preparation method comprises the following steps: growing graphene on a metal substrate, wherein the metal substrate comprises two metals with different capacities of catalyzing the growth of graphene, and the edge of the graphene is formed at the interface of the two metals. According to the invention, the graphene with high edge density is prepared by constructing the interface of two metals with different capabilities of catalyzing and growing the graphene, and the integrated material formed by compounding the graphene and the metal substrate has the characteristics of strong ion storage capability, high conductivity and good chemical and physical stability, and is suitable for being used as an electrochemical functional electrode material.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a preparation method of an edge-rich graphene-metal composite electrode material and the composite electrode material.
Background
The graphene has a two-dimensional carbon monoatomic layer in honeycomb regular hexagon arrangement, has high specific surface, high hardness, high transparency, excellent electric and heat conducting properties and excellent chemical stability, and has numerous advantages, so that the graphene is suitable for being applied to the field of wide materials, is a new material with important strategic significance, and is known as 'black metal' and 'universal material'. Graphene is listed as an advanced functional material by the thirteen-five national science and technology innovation program (abbreviated as the thirteen-five program). The graphene is used as a functional electrode material, and has high application value in the fields of rechargeable batteries, supercapacitors, fuel cells, biosensors and the like. The physical structure of the two-dimensional graphene is divided into a basal plane and an edge, and the edge carbon atoms have unpaired electrons, so that the difference between the physical and chemical properties of the two-dimensional graphene and the basal plane carbon atoms is large. Theoretical calculations and experiments reveal this. Therefore, the development of the preparation method of the edge-rich graphene has important practical significance. A method for preparing a large-area graphene material on a metal catalytic substrate by using a Chemical Vapor Deposition (CVD) method has been developed, and the graphene material is tightly connected with the metal substrate in a seamless and atomic manner, and has very high structural stability and electrical conductivity.
However, graphene grown on the same metal substrate has a low edge density, resulting in poor performance in applications as electrodes.
Disclosure of Invention
The invention aims to provide a preparation method of an edge-rich graphene-metal composite electrode material and the composite electrode material.
In order to achieve the above object, the present invention provides a preparation method of an edge-rich graphene-metal composite electrode material, including:
growing graphene on a metal substrate, wherein the metal substrate comprises a metal interface formed by two metals with different capacities of catalyzing the growth of graphene.
Optionally, the two metals with different abilities to catalyze the growth of graphene in the metal substrate include the following combinations:
Ni-Au, Ni-Cu, Ni-Ag, Ni-Fe, Ni-Co, Ni-Pd, Cu-Au, Cu-Ag, Cu-Pd, Cu-Co, Cu-Fe, Co-Ag, Co-Au or Co-Pd.
Optionally, the metal interface is structured by at least one method selected from chemical deposition, electrochemical deposition and vacuum sputtering.
Optionally, the graphene is grown on the metal substrate by using a chemical vapor deposition method.
Optionally, the chemical vapor deposition method is an atmospheric pressure chemical vapor deposition method and/or a plasma enhanced chemical vapor deposition method.
Optionally, the conditions of the chemical vapor deposition method include: the temperature is 300-1200 ℃, and the carbon source gas comprises one or more selected from methane, ethane, ethylene, acetylene and propyne for 1 second-12 hours.
The invention also provides the edge-rich graphene-metal composite electrode material prepared by the preparation method.
The invention has the following advantages:
the invention creatively provides a method for controlling the generation of the edge of the graphene by utilizing a bimetallic interface, the method is simple, the obtained edge-rich graphene-metal composite material has a stable structure and excellent conductivity, is suitable for being used as an electrode material of devices such as a lithium ion battery, a super capacitor, a chemical sensor and the like, can greatly enhance the performance of related applications, and has better practical application prospect.
Drawings
Fig. 1 is a schematic structural diagram of a specific embodiment of an edge-rich graphene-metal composite electrode material provided by the invention.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The invention provides a preparation method of an edge-rich graphene-metal composite electrode material, which comprises the following steps: growing graphene on a metal substrate, wherein the metal substrate comprises a metal interface formed by two metals with different capacities of catalyzing the growth of graphene. The traditional CVD method for growing graphene uses a single metal as a substrate, so that the edge density of the graphene material is low. The invention provides a new method, namely, the edge of the growing graphene is controlled by utilizing metal interfaces with different capabilities of catalyzing the growing graphene. The interface refers to the place where two metals are closely connected, and comprises a plane and a three-dimensional stereo form. That is, under the same CVD conditions, graphene is easily grown on one metal and not on the other metal, thus causing inconsistency in the thickness of the grown graphene at the interface of the two metals, or graphene is present on the surface of one metal and not on the surface of the other metal, resulting in the formation of graphene edges.
As shown in fig. 1, the present invention first constructs a metal interface of metals with different abilities to catalyze and grow graphene, namely weak catalytic metal 100 and strong catalytic metal 200, and the thicknesses of graphene layers 1 that can grow on the surfaces of the two metals are different under the same condition, so that an edge 11 is exposed at the interface of the two metals.
The two metals with different abilities to catalyze and grow graphene in the metal substrate of the present invention refer to metals capable of growing graphene with different thicknesses under the same conditions, and may include the following combinations, for example: Ni-Au, Ni-Cu, Ni-Ag, Ni-Fe, Ni-Co, Ni-Pd, Cu-Au, Cu-Ag, Cu-Pd, Cu-Co, Cu-Fe, Co-Ag, Co-Au or Co-Pd, wherein the Chinese names of Cu, Ni, Co, Pd, Pt, Rh, Au, Ag and Fe are copper, nickel, cobalt, palladium, platinum, rhodium, gold, silver and iron respectively.
The method of constructing the metal interface may be performed in various manners, for example, the metal interface may be constructed in at least one manner selected from the group consisting of chemical deposition, electrochemical deposition, and vacuum sputtering. The method can select one metal as an active substrate of the high catalytic growth graphene, and then deposit another metal with low catalytic growth graphene activity on or beside the substrate, so as to generate an interface of the two metals.
The graphene growing method can be performed by a conventional method, for example, the graphene can be grown on the metal substrate by a chemical vapor deposition method, which can be an atmospheric pressure chemical vapor deposition method and/or a plasma enhanced chemical vapor deposition method, and the temperature range of the chemical vapor deposition method for preparing the graphene is 300-; the carbon source gas used includes methane, ethane, ethylene, acetylene, propyne, etc.; the deposition steps are generally: the method comprises the steps of putting a metal substrate material into a quartz tube sealed on a tube furnace, vacuumizing, introducing hydrogen and protective gas (usually argon) to remove oxides on the surface of the metal substrate, introducing carbon source gas, and continuing at a carbonization temperature (300-. And after the graphene grows, continuously introducing argon until the sample is cooled to room temperature, opening the quartz tube, and taking out the sample to obtain the edge-rich graphene-metal composite electrode material.
The invention also provides the edge-rich graphene-metal composite electrode material prepared by the preparation method.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
Examples
And carrying out electrochemical polishing on the Ni sheet, then tightly connecting an anodic aluminum oxide template (AAO) with the polished Ni sheet and assembling the anodic aluminum oxide template and the polished Ni sheet as a working electrode into a three-electrode system for carrying out metal electrochemical deposition, alternately depositing Au and Ni into nanopores of the AAO template by using commercial electroplating solution under the constant potential of-0.9V (reference electrode: Ag/AgCl), and dissolving the AAO template by using NaOH solution to obtain an upright nanorod array with an Au-Ni interface. After vacuum drying, the nanorod array film was placed in a quartz tube of a CVD tube furnace, heated to 600 ℃ over 1 hour, and then a mixed gas of hydrogen and argon (flow rate ratio 1:2, pressure 0.001 atm) was introduced for 10 seconds. Then, acetylene gas was introduced under the same pressure for 10 seconds. Heating was stopped and argon was continued until the sample reached room temperature. Thus, the edge-rich graphene-metal nanorod array composite electrode material is prepared.
The prepared edge-rich graphene-multi-section Au-Ni nanorod array electrode material is used as a lithium ion battery cathode material, a lithium sheet is used as an anode, and the battery is obtained through cyclic charge and discharge tests, and the battery capacity is about 4000mAh/g through the test of a graphene electrode with 18 Au-Ni metal interfaces. Meanwhile, after 500 times of constant current charging and discharging, the battery capacity is kept above 95%, and the battery has better stability.
Comparative example
The preparation method is basically the same as that of example 1, except that the electrode material does not have an Au-Ni bimetallic interface, but a single metal Ni.
The prepared graphene-Ni nanorod array composite electrode material is used as a negative electrode material of a lithium ion battery, a lithium sheet is used as a positive electrode, and the battery capacity obtained through a cyclic charge-discharge test is about 800mAh/g, which is one fifth of the battery capacity of a nanorod array electrode material with 18 metal interfaces. The comparative experiment shows that: the graphene edge generated at the bimetallic interface significantly enhances the performance of the lithium ion battery.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. A preparation method of an edge-rich graphene-metal composite electrode material is characterized by comprising the following steps:
growing graphene on a metal substrate, wherein the metal substrate comprises a metal interface formed by two metals with different capacities of catalyzing the growth of graphene, so that the thickness of the grown graphene at the interface of the two metals is inconsistent.
2. The preparation method according to claim 1, wherein the two metals with different capacities of catalyzing the growth of graphene in the metal substrate comprise the following combinations:
Ni-Au, Ni-Cu, Ni-Ag, Ni-Fe, Ni-Co, Ni-Pd, Cu-Au, Cu-Ag, Cu-Pd, Cu-Co, Cu-Fe, Co-Ag, Co-Au or Co-Pd.
3. The method of claim 1, wherein the metal interface is structured by at least one method selected from the group consisting of chemical deposition, electrochemical deposition, and vacuum sputtering.
4. The method according to claim 1, wherein the graphene is grown on the metal substrate by chemical vapor deposition.
5. The method according to claim 4, wherein the chemical vapor deposition method is an atmospheric pressure chemical vapor deposition method and/or a plasma-enhanced chemical vapor deposition method.
6. The production method according to claim 4, wherein the conditions of the chemical vapor deposition method include: the temperature is 300-1200 ℃, the carbon source gas comprises one or more selected from methane, ethane, ethylene, acetylene and propyne, and the deposition time is 1 second-12 hours.
7. The edge-rich graphene-metal composite electrode material prepared by the preparation method of any one of claims 1 to 6.
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| CN111356329A (en) * | 2018-12-21 | 2020-06-30 | 惠州昌钲新材料有限公司 | Thin high-conductivity heat-dissipation composite material with low interface thermal resistance |
| CN109742379A (en) * | 2019-01-28 | 2019-05-10 | 哈工大机器人（岳阳）军民融合研究院 | It is a kind of on Si/C composite material grow graphene method, utilize material made from this method and its application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007926A (en) * | 2012-12-06 | 2013-04-03 | 浙江大学 | Preparation method of platinum/vertical graphene composite material electrocatalyst |
| CN105448528A (en) * | 2015-10-27 | 2016-03-30 | 梧州三和新材料科技有限公司 | Preparation method for metal-graphene composite porous electrode material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007926A (en) * | 2012-12-06 | 2013-04-03 | 浙江大学 | Preparation method of platinum/vertical graphene composite material electrocatalyst |
| CN105448528A (en) * | 2015-10-27 | 2016-03-30 | 梧州三和新材料科技有限公司 | Preparation method for metal-graphene composite porous electrode material |
Non-Patent Citations (2)
| Title |
|---|
| 铜基底化学气相沉积石墨烯的研究现状与展望;喻佳丽 等;《材料导报》;20150110;第29卷(第1期);第66-71页 * |
| 铜镍合金催化制备大面积均匀的少层石墨烯;刘平 等;《材料科学与工程学报》;20141020;第32卷(第5期);第630页左栏倒数第1段 * |
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